Atmospheric Chemistry and Physics

Preface to the First Edition xxiii
Preface to the Third Edition xxv
PART I | The Atmosphere and Its Constituents
Chapter 1 | The Atmosphere 3
1.1 History and Evolution of Earth's Atmosphere 3
1.2 Climate 5
1.3 Layers of the Atmosphere 5
1.4 Pressure in the Atmosphere 7
1.5 Temperature in the Atmosphere 10
1.6 Expressing the Amount of a Substance in the Atmosphere 10
1.7 Airborne Particles 14
1.8 Spatial and Temporal Scales of Atmospheric Processes 14
Problems 16
References 17
Chapter 2 | Atmospheric Trace Constituents 18
2.1 Atmospheric Lifetime 19
2.2 Sulfur-Containing Compounds 23
2.3 Nitrogen-Containing Compounds 27
2.4 Carbon-Containing Compounds 32
2.5 Halogen-Containing Compounds 40
2.6 Atmospheric Ozone 44
2.7 Particulate Matter (Aerosols) 47
2.8 Mercury 55
2.9 Emission Inventories 55
Appendix 2.1 US Air Pollution Legislation 56
Appendix 2.2 Hazardous Air Pollutants (Air Toxics) 57
Problems 59
References 61
PART II | Atmospheric Chemistry
Chapter 3 | Chemical Kinetics 69
3.1 Order of Reaction 69
3.2 Theories of Chemical Kinetics 71
3.3 The Pseudo-Steady-State Approximation 76
3.4 Reactions of Excited Species 77
3.5 Termolecular Reactions 78
3.6 Chemical Families 81
3.7 Gas-Surface Reactions 83
Problems 84
References 87
Chapter 4 | Atmospheric Radiation and Photochemistry 88
4.1 Radiation 88
4.2 Radiative Flux in the Atmosphere 91
4.3 Beer . Lambert Law and Optical Depth 93
4.4 Actinic Flux 95
4.5 Atmospheric Photochemistry 97
4.6 Absorption of Radiation by Atmospheric Gases 100
4.7 Absorption by O2 and O3 105
4.8 Photolysis Rate as a Function of Altitude 109
4.9 Photodissociation of O3 to Produce O and O(1D) 112
4.10 Photodissociation of NO2 114
Problems 117
References 117
Chapter 5 | Chemistry of the Stratosphere 119
5.1 Chapman Mechanism 122
5.2 Nitrogen Oxide Cycles 129
5.3 HOx Cycles 134
5.4 Halogen Cycles 139
5.5 Reservoir Species and Coupling of the Cycles 144
5.6 Ozone Hole 146
5.7 Heterogeneous (Nonpolar) Stratospheric Chemistry 155
5.8 Summary of Stratospheric Ozone Depletion 162
5.9 Transport and Mixing in the Stratosphere 165
5.10 Ozone Depletion Potential 167
Problems 168
References 173
Chapter 6 | Chemistry of the Troposphere 175
6.1 Production of Hydroxyl Radicals in the Troposphere 176
6.2 Basic Photochemical Cycle of NO2, NO, and O3 179
6.3 Atmospheric Chemistry of Carbon Monoxide 181
6.4 Atmospheric Chemistry of Methane 188
6.5 The NOx and NOy Families 192
6.6 Ozone Budget of the Troposphere and Role of NOx 195
6.7 Tropospheric Reservoir Molecules 203
6.8 Relative Roles of VOC and NOx in Ozone Formation 208
6.9 Simplified Organic/NOx Chemistry 212
6.10 Chemistry of Nonmethane Organic Compounds in the Troposphere 214
6.11 Atmospheric Chemistry of Biogenic Hydrocarbons 233
6.12 Atmospheric Chemistry of Reduced Nitrogen Compounds 244
6.13 Atmospheric Chemistry (Gas Phase) of Sulfur Compounds 246
6.14 Tropospheric Chemistry of Halogen Compounds 249
6.15 Atmospheric Chemistry of Mercury 253
Appendix 6 Organic Functional Groups 254
Problems 256
References 259
Chapter 7 | Chemistry of the Atmospheric Aqueous Phase 265
7.1 Liquid Water in the Atmosphere 265
7.2 Absorption Equilibria and Henry's Law 268
7.3 Aqueous-Phase Chemical Equilibria 271
7.4 Aqueous-Phase Reaction Rates 284
7.5 S(IV)-S(VI) Transformation and Sulfur Chemistry 286
7.6 Dynamic Behavior of Solutions with Aqueous-Phase Chemical Reactions 295
Appendix 7.1 Thermodynamic and Kinetic Data 301
Appendix 7.2 Additional Aqueous-Phase Sulfur Chemistry 305
7A.1 S(IV) Oxidation by the OH Radical 305
7A.2 Oxidation of S(IV) by Oxides of Nitrogen 308
7A.3 Reaction of Dissolved SO2 with HCHO 309
Appendix 7.3 Aqueous-Phase Nitrite and Nitrate Chemistry 311
7A.4 NOx Oxidation 311
7A.5 Nitrogen Radicals 311
Appendix 7.4 Aqueous-Phase Organic Chemistry 312
Appendix 7.5 Oxygen and Hydrogen Chemistry 313
Problems 314
References 317
PART III | Aerosols
Chapter 8 | Properties of the Atmospheric Aerosol 325
8.1 The Size Distribution Function 325
8.2 Ambient Aerosol Size Distributions 342
8.3 Aerosol Chemical Composition 352
8.4 Spatiotemporal Variation 354
Problems 357
References 359
Chapter 9 | Dynamics of Single Aerosol Particles 362
9.1 Continuum and Noncontinuum Dynamics: the Mean Free Path 362
9.2 The Drag on a Single Particle: Stokes' Law 368
9.3 Gravitational Settling of an Aerosol Particle 372
9.4 Motion of an Aerosol Particle in an External Force Field 376
9.5 Brownian Motion of Aerosol Particles 376
9.6 Aerosol and Fluid Motion 385
9.7 Equivalent Particle Diameters 388
Problems 393
References 394
Chapter 10 | Thermodynamics of Aerosols 396
10.1 Thermodynamic Principles 396
10.2 Aerosol Liquid Water Content 409
10.3 Equilibrium Vapor Pressure Over a Curved Surface: the Kelvin Effect 419
10.4 Thermodynamics of Atmospheric Aerosol Systems 423
10.5 Aerosol Thermodynamic Models 440
Problems 442
References 443
Chapter 11 | Nucleation 448
11.1 Classical Theory of Homogeneous Nucleation: Kinetic Approach 449
11.2 Classical Homogeneous Nucleation Theory: Constrained Equilibrium Approach 457
11.3 Recapitulation of Classical Theory 464
11.4 Experimental Measurement of Nucleation Rates 465
11.5 Modifications of the Classical Theory and More Rigorous Approaches 467
11.6 Binary Homogeneous Nucleation 468
11.7 Binary Nucleation in the H2SO4-H2O System 473
11.8 Nucleation on an Insoluble Foreign Surface 475
11.9 Ion-Induced Nucleation 478
11.10 Atmospheric New-Particle Formation 480
Appendix 11 The Law of Mass Action 487
Problems 489
References 490
Chapter 12 | Mass Transfer Aspects of Atmospheric Chemistry 493
12.1 Mass and Heat Transfer to Atmospheric Particles 493
12.2 Mass Transport Limitations in Aqueous-Phase Chemistry 503
12.3 Mass Transport and Aqueous-Phase Chemistry 511
12.4 Mass Transfer to Falling Drops 526
12.5 Characteristic Time for Atmospheric Aerosol Equilibrium 527
Appendix 12 Solution of the Transient Gas-Phase Diffusion Problem: Equations (12.4)-(12.7) 532
Problems 533
References 535
Chapter 13 | Dynamics of Aerosol Populations 537
13.1 Mathematical Representations of Aerosol Size Distributions 537
13.2 Condensation 538
13.3 Coagulation 544
13.4 The Discrete General Dynamic Equation 557
13.5 The Continuous General Dynamic Equation 558
Appendix 13.1 Additional Mechanisms of Coagulation 560
13A.1 Coagulation in Laminar Shear Flow 560
13A.2 Coagulation in Turbulent Flow 560
13A.3 Coagulation from Gravitational Settling 561
13A.4 Brownian Coagulation and External Force Fields 562
Appendix 13.2 Solution of (13.73) 567
Problems 568
References 571
Chapter 14 | Atmospheric Organic Aerosols 573
14.1 Chemistry of Secondary Organic Aerosol Formation 574
14.2 Volatility of Organic Compounds 582
14.3 Idealized Description of Secondary Organic Aerosol Formation 583
14.4 Gas-Particle Partitioning 590
14.5 Models of SOA Formation and Evolution 596
14.6 Primary Organic Aerosol 605
14.7 The Physical State of Organic Aerosols 608
14.8 SOA Particle-Phase Chemistry 610
14.9 Aqueous-Phase Secondary Organic Aerosol Formation 615
14.10 Estimates of the Global Budget of Atmospheric Organic Aerosol 622
Problems 623
References 626
Chapter 15 | Interaction of Aerosols with Radiation 633
15.1 Scattering and Absorption of Light by Small Particles 633
15.2 Visibility 644
15.3 Scattering, Absorption, and Extinction Coefficients From Mie Theory 647
15.4 Calculated Visibility Reduction Based on Atmospheric Data 651
Appendix 15 Calculation of Scattering and Extinction Coefficients by Mie Theory 654
Problems 654
References 656
PART IV | Physical and Dynamic Meteorology, Cloud Physics, and Atmospheric Diffusion
Chapter 16 | Physical and Dynamic Meteorology 661
16.1 Temperature in the Lower Atmosphere 661
16.2 Atmospheric Stability 665
16.3 The Moist Atmosphere 670
16.4 Basic Conservation Equations for the Atmospheric Surface Layer 683
16.5 Variation of Wind with Height in the Atmosphere 692
Appendix 16.1 Properties of Water and Water Solutions 701
16A.1 Specific Heat of Water and Ice 701
16A.2 Latent Heats of Vaporization and Melting for Water 701
16A.3 Water Surface Tension 701
Appendix 16.2 Derivation of the Basic Equations of Surface-Layer Atmospheric Fluid Mechanics 702
Problems 705
References 706
Chapter 17 | Cloud Physics 708
17.1 Equilibrium of Water Droplets in the Atmosphere 708
17.2 Cloud and Fog Formation 719
17.3 Growth Rate of Individual Cloud Droplets 723
17.4 Growth of a Droplet Population 726
17.5 Cloud Condensation Nuclei 730
17.6 Cloud Processing of Aerosols 736
17.7 Other Forms of Water in the Atmosphere 743
Appendix 17 Extended Köhler Theory 751
17A.1 Modified Form of Köhler Theory for a Soluble Trace Gas 751
17A.2 Modified Form of Köhler Theory for a Slightly Soluble Substance 754
17A.3 Modified Form of Köhler Theory for a Surface-Active Solute 755
17A.4 Examples 756
Problems 759
References 760
Chapter 18 | Atmospheric Diffusion 763
18.1 Eulerian Approach 763
18.2 Lagrangian Approach 766
18.3 Comparison of Eulerian and Lagrangian Approaches 767
18.4 Equations Governing the Mean Concentration of Species in Turbulence 767
18.5 Solution of the Atmospheric Diffusion Equation for an Instantaneous Source 771
18.6 Mean Concentration from Continuous Sources 772
18.7 Statistical Theory of Turbulent Diffusion 778
18.8 Summary of Atmospheric Diffusion Theories 783
18.9 Analytical Solutions for Atmospheric Diffusion: the Gaussian Plume Equation and Others 784
18.10 Dispersion Parameters in Gaussian Models 791
18.11 Plume Rise 796
18.12 Functional Forms of Mean Windspeed and Eddy Diffusivities 798
18.13 Solutions of the Steady-State Atmospheric Diffusion Equation 803
Appendix 18.1 Further Solutions of Atmospheric Diffusion Problems 807
18A.1 Solution of (18.29)-(18.31) 807
18A.2 Solution of (18.50) and (18.51) 809
18A.3 Solution of (18.59)-(18.61) 810
Appendix 18.2 Analytical Properties of the Gaussian Plume Equation 811
Problems 815
References 823
PART V | Dry and Wet Deposition
Chapter 19 | Dry Deposition 829
19.1 Deposition Velocity 829
19.2 Resistance Model for Dry Deposition 830
19.3 Aerodynamic Resistance 834
19.4 Quasilaminar Resistance 835
19.5 Surface Resistance 839
19.6 Measurement of Dry Deposition 849
19.7 Some Comments on Modeling and Measurement of Dry Deposition 851
Problems 852
References 854
Chapter 20 | Wet Deposition 856
20.1 General Representation of Atmospheric Wet Removal Processes 856
20.2 Below-Cloud Scavenging of Gases 860
20.3 Precipitation Scavenging of Particles 868
20.4 In-Cloud Scavenging 873
20.5 Acid Deposition 874
20.6 Acid Deposition Process Synthesis 878
Problems 881
References 886
PART VI | The Global Atmosphere, Biogeochemical Cycles, and Climate
Chapter 21 | General Circulation of the Atmosphere 891
21.1 Hadley Cell 893
21.2 Ferrell Cell and Polar Cell 893
21.3 Coriolis Force 895
21.4 Geostrophic Windspeed 897
21.5 The Thermal Wind Relation 902
21.6 Stratospheric Dynamics 905
21.7 The Hydrologic Cycle 905
Problems 906
References 907
Chapter 22 | Global Cycles: Sulfur and Carbon 908
22.1 The Atmospheric Sulfur Cycle 908
22.2 The Global Carbon Cycle 912
22.3 Solution for a Steady-State Four-Compartment Model of the Atmosphere 923
Problems 927
References 929
Chapter 23 | Global Climate 931
23.1 Earth's Energy Balance 931
23.2 Radiative Forcing 933
23.3 The Greenhouse Effect 936
23.4 Climate-Forcing Agents 942
23.5 Cosmic Rays and Climate 949
23.6 Climate Sensitivity 950
23.7 Simplified Dynamic Description of Climate Forcing and Response 951
23.8 Climate Feedbacks 955
23.9 Relative Radiative Forcing Indices 960
23.10 Atmospheric Chemistry and Climate Change 961
23.11 Conclusion 964
Problems 965
References 967
Chapter 24 | Aerosols and Climate 970
24.1 Scattering-Absorbing Model of an Aerosol Layer 972
24.2 Cooling Versus Heating of an Aerosol Layer 975
24.3 Scattering Model of an Aerosol Layer for a Nonabsorbing Aerosol 977
24.4 Upscatter Fraction 979
24.5 Optical Depth and Column Forcing 981
24.6 Internal and External Mixtures 985
24.7 Top-of-the-Atmosphere Versus Surface Forcing 987
24.8 Indirect Effects of Aerosols on Climate 990
Problems 1004
References 1004
PART VII | Chemical Transport Models and Statistical Models
Chapter 25 | Atmospheric Chemical Transport Models 1011
25.1 Introduction 1011
25.2 Box Models 1014
25.3 Three-Dimensional Atmospheric Chemical Transport Models 1020
25.4 One-Dimensional Lagrangian Models 1024
25.5 Other Forms of Chemical Transport Models 1026
25.6 Numerical Solution of Chemical Transport Models 1031
25.7 Model Evaluation 1046
25.8 Response of Organic and Inorganic Aerosols to Changes in Emission 1047
Problems 1048
References 1050
Chapter 26 | Statistical Models 1051
26.1 Receptor Modeling Methods 1051
26.2 Chemical Mass Balance (CMB) 1054
26.3 Factor Analysis 1059
26.4 Methods Incorporating Wind Information 1067
26.5 Probability Distributions for Air Pollutant Concentrations 1072
26A.1 The Lognormal Distribution 1073
26A.2 The Weibull Distribution 1074
26.6 Estimation of Parameters in the Distributions 1074
26A.1 Method of Quantiles 1075
26A.2 Method of Moments 1076
26.7 Order Statistics of Air Quality Data 1078
26A.1 Basic Notions and Terminology of Order Statistics 1078
26A.2 Extreme Values 1079
26.8 Exceedances of Critical Levels 1080
26.9 Alternative Forms of Air Quality Standards 1080
26.10 Relating Current and Future Air Pollutant Statistical Distributions 1083
Problems 1085
References 1087
Appendixes
Appendix A: | Units and Physical Constants 1091
A.1 SI Base Units 1091
A.2 SI Derived Units 1092
A.3 Fundamental Physical Constants 1094
A.4 Properties of the Atmosphere and Water 1094
A.5 Units for Representing Chemical Reactions 1096
A.6 Concentrations in the Aqueous Phase 1096
A.7 Symbols Denoting Concentration 1097
References 1097
Appendix B: | Rate Constants of Atmospheric Chemical Reactions 1098
References 1106
Appendix C: | Abbreviations 1107
Index 1112